Plastic composition and process of making same.



UNHEU s ra grns Par, v

LAWRENCE V. REDMAN, OF LAWEENCE, KANSAS, ASSIGNOR TO-BEDMANOL CHEMICALPRODUCTS COMPANY, OF CHICAGO, ILLINOIS, A CORPORATION OF WEST VIRGINIA.

rms'rxc COMPOSITION AND rnocnss or name SAME;

No Drawing.

I To all whom 2'23 may concern:

Be it known that I, LAWRENCE V. RED-4 MAN, a citizen of the UnitedStates, residing at'Lawrence, in the county of Douglas and State ofKansas, have inventeda new and useful Improvement in Plastic Compositionand Processes of Making Same, of which the i} following is aspecification.

This invention relates particularly to a composition of matter andprocess ofpro ducing the same; and1 the primary object of 'the inventionis to provide anew composition of matter adapted-to various uses.

In one form the new composition of matter; is. adapted to serve as animproved I lacquer or varnish which can be applied to serveas apreservative. for the surfaces of I 'wood, metal, and other materials;and the new composition of matter, is also adapted to serve as a hinder,or as a glue, or other adhesive.

The new substance may be used advanta'geously as a binder for abrasivematerials, such asvcarborundum or aluminum oxid. Also, it" may beemployed in the manufacture of artificial wood, as where the mateif-ialis' mixed with sawdust or wood fiber and pressed into any desired form.Again, the material unay have mixed therewith a pigment, sand or otherneutral material and in this condition may be used for coating or,

painting purposes. contemplated.

. In its final stagethe new product is insoluble in any of the solventsso known, such Various other uses are as acetone, amyl acetate,nitrobenzene, ethylalso may be used for making molding-blocks or'diesfor many purposes where such'mate1 rial is desirable. p I

The new composition of matter is preferably compounded or produced bymixing. a quantity of a phenolic body, a lesser quantity ofhexamethylenetetramin, and a quantity of anisol approximately the samenum- Specification of Letters Patent. Application and Apr1l4, i912,Serial iroI ettented Dec. n, rain. ,e'ze.

ber of formula weights as that of the hexamethylenetetramin, andsubjecting the "same to a heating process, which results in theelimination of ammonia and in the rproduction of a compound having analkylated hydroxyl group in its molecule and possessing the ethercharacteristic of sistance to decomposition.

In carrying out the improved process, it is preferredto employ thefollowing proportions of materials and steps, that is'to say: Take sixformula weights, or-molecul r weights, of a phenolic body, such as carbo1c acid (C H OH) one formula weight, or

molecular weight, of hexamethylenetetramin ((CH,) N,) one formulaweight, or molecular weight, anisol QC H OCHQ; sub ect the great re- Hmixture to the actioi'fof heat at a'tem-perature of from 100 C. to 140Cffor, say, from fifteen minutes to several hours, dependmg upon thequantity of materials being treated and the temperature. This may bedone in an 7 open vessel, and as the application of heat continues,ammonia is given 011'. Under this method of treatment, the mixture soonchanges its condition to a yellowish transparent mobile liquid, whichfinally becomes.

viscous and solidifies on cooling. The product thus obtained is soluble'in certain s'olvents, such as acetone and others named above, ormixtures of the same, and when thus dissolved the material may be usedas a varnish. After being applied in a thin coatinn and allowed to standfor some time, it

, will serve as a solvent for the product. This course may beparticularly desirable where a very thin varnish is deslred. Ordmarydenatured alcohol will serve the purpose.'-

Where the alcohol is introduced before the heating it will serve tocontrol the reaction heating is performed in the absence of a solvent, ametal object, forinstance, may be immersed while the liquid is in a veryfluid condition, and the' surfaces may thus be coated .or lacquered, andafterward dried to harden the coatings; or the lacqueringor byregulating the temperature. Where the be increased to atemperature of,say, 180

' heat applied the longer the period required tion of t imately thedesired shape,

0. and continued for a time, when the material will pass to the finalstage, in which condition it is an amorp ous mass, hard, highlyresilient, of high tenacity, insoluble in the known solvents and inordinary acids and alkalis, and chemically and physically inert to ahigh degree. 4

In its final stage the material is a most excellent non-conductor'ofboth electricity and heat. The length of time required to convert thematerialto the final stage (depends upon the quantity of materialtreated and the degree of heat applied. During the first heat treatment,ammonia is given off in very a preciable quantities; and'at the end oftlib first heat treatment, if the material be allowed to become solid,it possesses a clear light yellowish color and is brittle andtransparent. The color may be varied by varying the treatment, e. 9.,the length of time of heating, degree of heating, and pro portion ofingredients. Thus, an excess of hexamethylenetetramin produces a lightercolored product; an excess of phenol produces a product of darker color;and an excess of anisol causes-the product to be transformed morerapidly and produces a lighter color. In converting the material to thefinal insoluble stage, the lower the degree of to eifec't theconversion. When it is desired to produce a molded block or objectcomposed of the new product, this may be accomplished by takingapproximately 80 per cent. of the insoluble material in mass andapproximately 20 per cent. of the soluble material in mass, grinding thesame together, then placing the powdered material m a hot mold,pressmg'the same into a proxthen reheating the mass to a plasticcondition, and then pressing in the mold to the final shape. The degreeof heat applied in this operation should ordinaril be sufiicient toconvert that por e material which is taken in the soluble state to theinsoluble state.

When the materials employed in producing the new composition of matterare carbolic acid, hexamethylenetetramin and anisol in approximately theproportions mentioned above, the product, in its final stage, may berepresented by the formula c,H,,oqH, c mocngrc npon l acter and iscarried on the non-reactivity of the final group, the

molecule cannot form an anhydrid or an inner anhydrid with itself, or alactone substance. It follows from the materials used and the stepsfollowed that no water is roduced in the reaction; and it ma be, dedthat water is not employed in t e mixture at the outset, except as itmay be present in comparatively small uantities as an im urity. Thereaction is t us anhydrous in c arabsence of water. I In place of theanisol'any suitable material may be employed which has its hydroxylhydrogen of the phenol group re'-- placed by a non-reactive group orradical. Otherwise stated, foranisol may be substituted any hydroxylatedaromatic derivative, which has had its hydroxyl radical, or the hydron'thereof, replaced by a non-reac tlve e ement or group. Such aderivative may be designated as an aromatic derivative having thegeneral formula-RX, where R represents an aromatic radical and X anon-reactive element or group. Where the hydrogen only of the hydroxylgroup is re-- practically in the anisol may be produced by thereacanisol, which is an ether, methyl benzoat (C H,,COOCH,,), which isan ester; or phenylmethyl ketone (C H CQGHQ that is, a ketone. I Otherinstances of ethers which may be used are phenetol (C H OC HQ andd1phenylox1d (C H OC H and other instances might be mentioned. If, forthe anisol, one were to substitute a substance lessreactive, such asbenzene, it would be necessary to carry on the process under pressure.

acid, one-may employ a homologue, such as While it is preferred toemploy carbolic cresol (CH G HpH), or other phenolic body whichexpression is to be understood as mcluding any suitable hydroxy-aromaticcompound. It is to be noted, however, that produce a directreactionbetween hexamethylenetetramin, or its equivalent, anisol, or itsequivalent, and a phenol in uncombmed condition; and as I obviate manydifliculties incident to any process which prod es a r y mbin grmaldehyde to obtain the advantageous results set forth herein.-

As a substitute for hexamethylenetetramm one may employ hydrobenzamid (CH CH) N which is a solid and which may be used in place of the solidhex-amethylenetetramin by substantially the same process describedabove. In fact, one may employ in lieu of the hexamethylenetetramm anycompound containing methylene, which is readily dissociated in orderthat the methylene group thereof may enter into the new composition. Theappended claims may be understood, therefore, where the termhexamethylenetetramin is employed, as including any equivalent for thissubstance which will produce the desired result. At the same time, it isnoted that the process is exceedingly simple and direct and free frommany objections Where the hexamethylenetetramin itself is employed as a'the group COCH It is tobe understood,

therefore, that in the appended claims, wherever is specified asubstance in which hydroxyl hydrogen is replaced by a non-reactivegroup, this expression should include all substitutes of a. cyclicnature (that is, ring compounds), but having the hydroxyl hydrogen,or-the hydroxyl group replaced by an inactive group, 0. g. by hydrogenitself, a keto group, an ester group, .etc., so that substances such asesters, ketones, and inactive substitution products of benzene are to beincluded.

The proportions of the ingredients may be varied; but, if the proportionof the phenolic body is greatly decreased, the condensation productbecomes brittle and less de-' sirable from a commercial standpoint, aswell as more expensive, so that it is impracticable to reduce theproportion of the phenolic body to less than two formula weights of thephenolic body to one formula weight of each of the other substances.

The foregoing detailed description has been given for clearness ofunderstanding only, and no undue limitation should be understoodtherefrom, but. the appended claims should be construed as broadly aspermissible in view of the prior art.

What I regard as new, and desire to secure by Letters Patent, is-

1. An amorphous condensation product of a phenolic body, an activemethylene body, and a derivative of a hydroxylated aromatic compoundhaving the general formula RX, where It represents an aromatic radicaland X a non-reactive element or group.

2. An amorphouscondensation product of a phenolic body, a methylene-aminbody in the form of a solid and in lesser proportion, and a derivativeof a hydroxylated aromatic compound having the general formula RX, whereR represents an aromatic radical and X a non-reactive element or group.r

3. An amorphous condensation product of a hydroxy aromatic compound, anactive methylene body containing nitrogen, and a derivative of ahydroxylated aroma-tic compound having the general formula RX, where Rrepresents an aromatic radical and X a non-reactive element or groupafter subjection to the action of heat and the elimination of nitrogenin the form of ammonia.

4. An amorphous condensation substance comprising the condensationproduct of a substantially anhydrous reaction between a phenolic body,an active methylene body,

, and a derivative of a hydroxylated aromatic compound having thegeneral formula RX, where R represents an aromatic radical and Xanon-reactive element or group, such reaction carried on substantiallyin the absence of water.

5. An amorphous condensation-product of a phenolic body,hexamethylenetetramin in solid form, and a derivative of a hydroxylatedaromatic compound having the general formula R-X, where R represents anarcmatic radical and X a non-reactive element or group. I

6. An amorphous condensation product of a-phenolic body, an activemethylene body, and a derivative of a h'ydroxylated aromatic compound,after subjection to the action of heat for a period of time at moderatetemperatureapp'rcximating 140 0., and after subjection to a higherdegree of heat approximating 180 C. 1

7. An amorphous condensation product 0 a phenolic body, an activemethylene body, and .anisol.

8. An amorphous condensation product of ap'henolic body,hexamethylenetetramm in solid form, and anisol.

9. An amorphous condensation product of a phenolic body,hexamethylenetetramm, and a derivative of a hydroxylated aromaticcompound having the formula RO--X, where R represents an aromaticradical, 0 represents oxygen, and X a non-reactive element or group,compounded in approximately the proportions of six molecular weights ofthe phenol body, one molecular weight of hexamethylenetetramin and oneformula weight of the third named substance.

10. An amorphous condensation product of an active methylene body, aderivative of a hydroxylated aromatic compound having the generalformula RX, where R represents an aromatic radical and X a non-reactiveelement or group, and a phenolic body, combined in the proportion ofmore than twice the number of molecular Weights of the phenolic body, tothe number of molecular Weights of either of the first two substancesmentioned.

11. The process of producing a condensation product, consisting ofmixing a phenolic body, a methylene-amin body and a derivative of ahydroxylated aromatic compound having the general formula RX, where Rrepresents an aromatic radical and X a nonreactive element or group, andsubjecting the same to the action of heat at a comparatively moderatetemperature, the heat treatment being continued until a homogeneoussoluble substance is produced. I

12. The process of producing a condensa-- tion product consisting inmixing a phenolic body, an active methylene body in smaller proportions,and a derivative of a hydroxylated aromatic compound having the generalformula li -X, where R represents an aromatic radical and X anon-reactive element or group, the last named substance in smallerproportion than the first-named substance, and subjecting the mixture tothe action of heat at a moderate temperature approximating.14.0 G.,'andthereafter sub ecting the resultant mass to a higher temperature ap--proximating 180 (1., the treatment at the higher temperature continuinguntil the mass becomes hardand insoluble.

13. The process of producing a condensation product, consistmg in mixinga phe- 'nolic body, an active methylene body in the form of a solidcontaining nitrogen and taken in lesser proportion, and a derivative,

the second and third named substances being used in considerably smallerproportions than the first-named substance, and sub.- jecting themixture to heat treatment to eliminate nitrogen in the form of ammoniaand produce a homogeneous compound.

15. The process of producing a condensation product consisting in mixinga phenolic body, a methylene-amin body and a derivative of ahydroxylated aromatic compound having the general formula RX, where Rrepresents an aromatic radical and X a non-reactive element or group,the second and third named substances being taken in smaller proportionsthan the firstnamed substance, subjecting the mixture to the action ofheat and adding a solvent as a step inthe process.

.16. The process of producing a condensation product consisting inmixing a phenolic body, an active methylene body in solid form, andanisol, subjecting the mixture to the action of heat, and adding asolvent as a step in the process.

17. The method of producing a condensation product, consistmg in mixinga phenolic ody, hexamethylenetetramin, and anisol in the approximateproportions of six molecular weights of the phenolic body, one molecularweight of the hexamethylenetetramin, and one molecular weight of theanisol, and subjecting the mixture to the action of heat to eliminatenitrogen in the form of ammonia and produce a homogeneous compound.

18. The process of producing a condensation product consisting in mixinga phenolic body which is not a'condensatlon prodnot, an active methylenebody, and a derivative of a hydroxylated aromatic compound having thegeneral formula RX, where R represents an aromatic radical and X anon-reactive element or group, and subjecting the mixture to the actionof heat while the mixture is exposed to the 'atmos phere.

19. The process of producing a phenolic condensation product consistingof mixing a phenolic body, hexamethylenetetramin, and a compound havingan alkalated hydroxyl group in its molecule, the last two substancesbeing in substantially equal proportions and the phenolic body being inmuch larger proportion than the other ingredients, introducing a solventwhich acts also as a reaction-controlling agent, and subjecting thewhole to the action of heat.

20. The method of producing a phenolic condensation product consistingin mixing a phenolic body, a methylene-amin body, and.

a derivative of a hydroxylated aromatic compound having the generalformula said mixture to cause anhydrous reaction substantially in theabsence of Water, Where R represents an aromatic radical and X anon-reactive element or-group.

21. The process of producing a condensation product consisting of mixinga hydroxy aromatic compound, an active methylene body, and a derivativeof a hydroxylated aromatic compound having the general formula B-X,where It represents an aromatic radical and X a nonreact1ve element orgroup, and subjecting the same, in the absence of water, to the actionof heat at a vcomparatively moderate temperature, the heat treatmentbeing continued until a homogeneous soluble substance is produced.

i 22. The process of producing a condensation product consisting ofmixing a phenolic body, an active methylene body in considerably smallerproportion, and a derivative of a hydroxylated aromatic compound havingthe general formula RX, where R represents an aromatic radical and X anon-reactive element or group, and then in considerably smallerproportion than the phenolic body, and subjecting the same to the actionof heat until a homogeneous soluble-substance is produced. LAWRENCE V.REDMAN. In presence of- R. A. RAYMOND, J. G. ANDERSON.

